CN101541912B - Method for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same - Google Patents

Method for preparing cerium oxide powder using organic solvent and cmp slurry comprising the same Download PDF

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CN101541912B
CN101541912B CN2007800431180A CN200780043118A CN101541912B CN 101541912 B CN101541912 B CN 101541912B CN 2007800431180 A CN2007800431180 A CN 2007800431180A CN 200780043118 A CN200780043118 A CN 200780043118A CN 101541912 B CN101541912 B CN 101541912B
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oxide powder
cerium oxide
solution
cerium
powder
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CN101541912A (en
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鲁埈硕
吴明焕
曹昇范
金种珌
金长烈
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LG Electronics Inc
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Abstract

Disclosed is a method for directly preparing cerium oxide powder in a solution phase by a) mixing a cerium precursor solution with a precipitant solution to cause a reaction; and b) performing oxidation treatment of the reacted solution, wherein at least one kind of pure organic solvent containing no water is used as a solvent for the cerium precursor solution as well as the precipitant solution to thereby prepare the cerium oxide powder, the particle size of which is adjusted to 50nm to 3 mum. Cerium oxide powder obtained from the method and CMP slurry comprising the cerium oxide powder as a polishing agent are also disclosed. The method makes it possible to prepare cerium oxide powder with an average particle size of 50nm or greater and high crystallinity, which is difficult to prepare by the conventional wet precipitation process, by using an organic solvent as a solvent in a wet precipitation process, and the so-prepared cerium oxide powder can be used as a polishing agent for CMP slurry even without being subjected to separate heat treatment.

Description

The CMP slurry that adopts organic solvent to prepare the method for cerium oxide powder and comprise this powder
Technical field
The present invention relates to a kind of through in wet method, adopting organic solvent to prepare the method for cerium oxide powder and comprise the CMP slurry of the cerium oxide powder of such preparation as rumbling compound.
Background technology
As well known in the art, cerium dioxide (CeO 2) be a kind of H.D stupalith; It is widely used in catalyzer, phosphor, makeup and the rumbling compound, and it has received concern as the rumbling compound of STI (shallow-trench isolation) method that is used for semiconducter device and as the rumbling compound of opticglass recently.Especially, adopting cerium dioxide (CeO 2) powder is as being used for the rumbling compound of CMP slurry; Press for synthetic uniform powder, but the solid phase method in the high temperature (owing to its high processing temperature is difficult to control size and dispersiveness) is only preparation cerium dioxide (CeO that is applicable in the present known industry with spherical particle shape and small grain size 2) method of powder.In addition, although, also have no one piece to report that it is the above monocrystalline cerium dioxide (CeO of 30nm that wet method can successfully be synthesized mean particle size like the multiple wet method of coprecipitation method, hydrothermal method, emulsion process etc. relatively easily control size and particle shape 2) powder.Therefore, in industry, utilize cerium dioxide (CeO 2) powder faces very big difficulty.
In recent years, the interest of the research of and commercial applications synthetic to ceramic powder is cumulative, this be receive below the prompting of understanding, the excellent properties that promptly makes full use of pottery receives the restriction of obtaining the ordinary method of powder through powder ore.Relevant therewith, owing to can therefore carry out positive research through remedying the ceramic product that the defective that has comminuting method now develop the new features of ceramic and obtain high added value to wet method like the wet method of the precipitator method, sol-gel method, hydrothermal method etc.
Particularly; Because the precipitator method can make crystal grain growth and can control size and particle shape in mutually at solution; Solution mutually in temperature be significantly less than the temperature in the solid state reaction; And because easy control size of the precipitator method and particle shape, this is the common advantage of all wet methods, therefore big quantity research concentrates on the precipitator method and commercial use thereof.Although because wet method is grown to serve as oarse-grained growth pattern (build-up manner) with small crystal nucleus and carries out, therefore comprise that the wet method of the precipitator method prepares fine particle easily, wet method is difficult to prepare the particle with volume particle size and high-crystallinity.
Many investigators attempt to address this problem; For example; Through using crystal seed after the initial initial granularity of control, to carry out crystal growth naturally; In the high temperature and high pressure reactions step of carrying out on the stagnation point of water under the supercritical state, perhaps adopt the acid/alkali of high density to be used to increase solubleness, but all these effort are all failed in commercial applications.Wherein, Adopt the supercutical fluid method of supercritical water to need to carry out the equipment that high temperature and high pressure reacts, these equipment are costliness and loss part very, and this method is difficult to control reaction conditions; Although therefore this method has been carried out successive research, still have very big distance from commercial applications.
At research cerium dioxide (CeO 2) in the instance of powdered preparation, people such as Matijevic have reported: through starting material being enclosed the Pyrex pipe, thereby the material of heated sealant is settled out cerous hydroxide under constant temperature, then at this throw out of about 600 ℃ temperature lower calcination, can be from by Ce (SO 4) 24H 2O, (NH 4) 4Ce (SO 4) 42H 2O, (NH 4) 2Ce (NO 3) 6The starting material of forming with other materials obtain hexagon sheet and globular cerium oxide particles (Wan Peter Hsu; Lena Roannquist; EgonMatijevic, Preparation and Properties of Monodispersed Colloidal Particles ofLanthanide Compounds.2.Cerium (IV), Langmuir; 4,31-37 (1988)).
At research cerium dioxide (CeO 2) in another instance of powdered preparation, people such as E.Tani are through by cerous nitrate and NH 4The starting material of OH are settled out oxyhydroxide; And under about 500 to 600 ℃ temperature, fire the oxyhydroxide that is settled out with multiple additives; And prepare the cerium oxide powder that mean particle size is 100 μ m (E Tani; M.Yoshimura, S Somiya, Crystallization and crystalgrowth of CeO 2Under hydrothermal consitions, Journal of the MaterialsScience Letters, 1,461-462, (1982)).
At research cerium dioxide (CeO 2) in another instance of powdered preparation, people such as Takuya Tsuzuki are through adopting mechanochemical reaction and calcination method by Cerium II Chloride (CeCl 3) and the NaOH raw material preparing cerium oxide powder of uniform nano-scale.When in elementary pulverising step, pulverizing wherein NaCl of cerium chloride and NaOH and adding, synthesized cerium hydroxide by mechanico-chemical reaction by steel ball.And,, thereby synthesized the spherical cerium dioxide of nano-scale at the temperature lower calcination synthetic cerous hydroxide more than 500 ℃.Yet be through the problem of the synthetic cerium oxide powder of such mechanochemical reaction: in the synthetic cerium oxide powder, contain a large amount of Na, Na is a pollutent serious in the semiconductor machining, therefore independent cleaning step must be arranged.And owing to the reunion and the crystallization that are caused by calcining step, being ground into nano-sized particles needs lot of energy.Therefore, with regard to its commercialization be applied to regard to the CMP method, many problems still have (Takuya Tsuzuki to be solved; Paul G, McCormick, Synthesis of Ultrafine Ceria Powders by Mechanochemical Processing; Journalof the American Ceramic Society; 84 (7), 1453-58, (2001)).
Therefore cerium oxide powder by above-mentioned precipitator method preparation also is restricted in the increase in granularity in crystal growth.Therefore, in the time will making granularity and be not less than the cerium oxide powder of specific dimensions, problem is: must correspondingly carry out solid phase method with the mode that preparation is equivalent to the oxyhydroxide of cerium dioxide intermediate product, at high temperature through thermal treatment it calcined then.
Summary of the invention
Therefore, made the present invention to the problems referred to above.Contriver of the present invention has been found that; Preparing in the cerium oxide powder through wet precipitation; Through adopting organic solvent as solvent; This method can prepare and has the above mean particle size of 50nm and the cerium oxide powder of high-crystallinity, and is difficult to prepare such powder through the wet precipitation of routine, even and also can the cerium oxide powder usefulness that prepare like this be acted on the rumbling compound of CMP slurry without independent thermal treatment.
Therefore, one object of the present invention be provide a kind of through in wet precipitation, adopt organic solvent prepare the method for cerium dioxide, through this method preparation cerium oxide powder and comprise the CMP slurry of the cerium oxide powder of such preparation as rumbling compound.
According to one embodiment of the invention, it provides a kind of and directly prepare the method for cerium oxide powder in mutually at solution, and this method comprises following step: a) the cerium precursor solution is mixed with precipitant solution and make and react generation; And b) solution to reaction carries out oxide treatment, wherein, at least a water-free pure organic solvent usefulness is acted on the solvent of cerium precursor solution and precipitant solution, thereby prepare cerium oxide powder, and the granularity of this powder is adjusted to 50nm to 3 μ m.
According to another embodiment of the invention, it provides the cerium oxide powder by method for preparing, and the amount of residual residue carbon is 0.1ppm to 100ppm above that or in it, and the granularity of this powder is 50nm to 3 μ m.
According to another embodiment of the present invention, it provides a kind of CMP slurry that comprises above-mentioned cerium oxide powder as rumbling compound.
Hereinafter, the present invention will be described in more detail.
Be combined to powder usually through two steps through solution, that is, and nucleation step and crystal growth step, and must control this two steps in order to regulate gained particulate size.For example, the quantity of nucleus is many more in the nucleation step, and gained particulate size is just more little.And, in crystal growth step, when degree of supersaturation height or nucleation energy barrier are low, be difficult to preparation greatly and homogeneous granules owing to secondary nucleation in crystal growth step, occurs.Therefore, in order to obtain the big and necessary degree of supersaturation of suitably controlling reaction soln of uniform gained particle of overall dimension.Because degree of supersaturation can mainly be controlled through the concentration of solute and the solubleness of solution; Therefore suitably regulate the solubleness of concentration, temperature of reaction and the solution of solvent types, solute, and the additive of suitably selecting to be used to control particle shape is important for the required ceramic powder of preparation.
According to the present invention, prepare mutually in the cerium oxide powder at solution, can prepare uniform cerium oxide powder through adopting organic solvent as the solvent that is used for cerium precursor solution and/or precipitant solution with volume particle size.
Every kind of solvent all has unique specific inductivity; And in the nucleation step and crystal growth step in the powdered preparation process; The specific inductivity of solvent causes the variation of surface energy, surface charge etc., thereby influences the reunion and the growth of nucleus, and therefore influences the size and dimension of gained powder.
The surface potential of dispersed particles (electrokinetic potential) is proportional in the specific inductivity of solvent and the solvent; And,, low electrokinetic potential reunites very apace so possibly causing between particle or nucleus because the particle or the nucleus that are generated by nucleation are in an unsure state because of exclusion property low between it.Thus, the magnitude of exclusion property is close to identically each other between particle or nucleus, so particle or nucleus can be agglomerated into the particle of uniform-dimension.Because through particle bonded process, for example strong agglomeration or Ostwald ripening are so the secondary granule of reuniting like this is grown to the particle of relatively large size according to the reaction conditions that comprises temperature, concentration etc. for primary granule or nucleus.
When water usefulness is acted on the solvent of liquid-phase precipitation of cerium oxide powder,, therefore be difficult to regulate the particulate size and dimension because particle tends to have the granularity less than 20nm.Yet; In the present invention, through only adopting the water-free pure organic solvent just can be with the size adjustment of powder particle to more than the 50nm, especially as solvent; Thereby regulate the specific inductivity of solvent through the multiple organic solvent that mutual mixing has a differing dielectric constant, also can regulate granularity.
The specific inductivity that is used as the organic solvent of solvent in the present invention is preferably 20 to 50.Specific inductivity demonstrates too high volatility less than 20 solvent and is difficult for being processed; And specific inductivity causes the high surface potential of particulate that generates through deposition greater than 50 solvent; Therefore and under stable status, keeping the particle of relative reduced size, this gives and increases granularity and brought problem.
As a reference, the specific inductivity of water is 80.37 (under 20 ℃).
The preferred embodiment of the organic solvent that can use in the present invention comprises:
25.3), propyl alcohol, butanols etc. 1) alcohol: methyl alcohol, the ethanol (specific inductivity under 20 ℃:.
41.4), Ucar 35, butyleneglycol etc. 2) glycol: the terepthaloyl moietie (specific inductivity under 20 ℃:.
3) ether: dme, ethyl-methyl ether, diethyl ether etc.
4) ester: methyl acetate, ETHYLE ACETATE, propyl acetate, butylacetate, methyl propionate, ethyl propionate etc.
5) ketone: acetone, ethyl methyl ketone, metacetone, MIBK etc.
6) other: formic acid etc.
Can be used alone or in combination this organic solvent.In addition, being used for the organic solvent of cerium precursor solution can be identical or different with the organic solvent that is used for precipitant solution.
In the method for preparing cerium oxide powder according to the present invention, thereby step a) makes the precipitation of hydroxide step of (wherein 3 valency ceriums mix with 4 valency ceriums) for the cerium precursor solution is mixed with precipitant solution.Can make sedimentary cerous hydroxide become cerium dioxide through follow-up oxidation treatment step.
There is not particular restriction to can be used for cerium precursor of the present invention, as long as it is the cerium compound that is dissolvable in water organic solvent, and the cerium precursor of the form of preferably salt.The limiting examples of cerium precursor comprises cerous nitrate, cerous acetate etc., and it can be used alone or in combination.
Through being dissolved in the organic solvent with the concentration of 0.01mol to 2mol, the cerium precursor can prepare the cerium precursor solution.If the concentration of cerium precursor solution is lower than above-mentioned concentration range, the productive rate of cerium oxide powder possibly descend.On the contrary, if the concentration of cerium precursor solution is higher than above-mentioned concentration range, the gained powder granularity that can become is inhomogeneous.
The kind that can be used for precipitation agent of the present invention has very big influence to the granularity and the percent crystallinity of gained powder.Yet, as long as this precipitation agent be can conditioned reaction pH value of solution value alkaline matter, just the kind to precipitation agent does not have particular restriction.The limiting examples of precipitation agent comprises KOH, NH 4OH etc., it can be used alone or in combination.
Can prepare precipitant solution through precipitation agent is dissolved in the organic solvent, and the concentration range of precipitant solution can be 0.5 to 5 times with the cerium precursor solution concentration range of this precipitant solution reaction.If the concentration of precipitant solution is lower than above-mentioned concentration range, possibly not precipitate.On the contrary, if the concentration of precipitant solution is higher than above-mentioned concentration range, the growth of powder possibly suppressed by too high nucleation rate.
In the method for preparing cerium oxide powder according to the present invention, thereby step b) is for carrying out the step of oxide treatment preparation cerium dioxide to the gained cerous hydroxide.Oxide treatment can realize through the following step: 1) in reaction soln, add oxygenant, 2) in reaction soln, be blown into oxygen-containing gas etc.The limiting examples of oxygenant comprises: like hydrogen peroxide (H 2O 2) or ammonium peroxydisulfate ((NH 4) 2S 2O 8) superoxide, like perchloric acid (HClO 4), permanganic acid (HMnO 4) or chromic acid (H 2CrO 4) alcohol acid etc.Based on the weight of cerium salt, can add the oxygenant of 1 to 100wt% amount.
Can be with the mixture of pure oxygen, oxygen and nitrogen, air etc. as oxygen-containing gas, and flow velocity that can 0.01 to 100cc/min is blown into oxygen-containing gas.
Temperature in the precipitin reaction process is preferably the temperature that extremely is not higher than solvent boiling point more than 30 ℃, can the stirring velocity in the precipitin reaction process be adjusted to 0 to 300rpm, and preferably carry out precipitin reaction 30 minutes to 60 hours.
Preferably, will carry out spinning and washing by the cerium oxide powder of this method preparation, dry 24 hours then.In order to remove the agglomerate of powder, the granularity of control powder is also removed meal, can also after drying, pass through ball mill, jet-type shredder etc. and suitably grind cerium oxide powder.
Cerium oxide powder by method preparation of the present invention has the mean particle size of 50nm to 3 μ m.
In addition, the cerium oxide powder by method preparation of the present invention can have 20m 2/ g to 250m 2The specific surface area of/g, and preferably, specific surface area is 50m 2/ g to 200m 2/ g.
Because cerium oxide powder of the present invention has aforesaid bigger specific surface area, in the CMP method, it can improve polishing rate through increasing with the contact area of wanting polished film.And because cerium oxide powder of the present invention has the granularity of control as stated, it possibly cause the macrobead of cut and can prevent tiny cut through thorough removal on polished film.
Simultaneously, because cerium oxide powder of the present invention is through being that the method for the present invention of characteristic prepares to adopt organic solvent, even therefore behind spinning, washing and drying step, organic solvent still can remain in the surface of cerium oxide powder or inner.Through can analyze remaining organic solvent with TOC measurement carbon residues such as (total organic carbons).For example, cerium oxide powder of the present invention can contain the carbon of 0.1ppm to 100ppm residual quantity.The carbon residue that is lower than above-mentioned surface analysis amount possibly be to be caused by analytical error, perhaps possibly be in the detection of adopting separately water to carry out under as the situation of solvent.
Cerium oxide powder through deposition, drying and pulverising step can be with it all with the rumbling compound that acts on the CMP slurry.Yet, consider the performance of powder, also can under 300 to 350 ℃ temperature, heat-treat 10 minutes to 6 hours to use this powder after removing the moisture that comprises in it fully.
Through being dispersed in can prepare in the solvent, cerium oxide powder and dispersion agent comprise the CMP slurry of cerium oxide powder as rumbling compound.
Can be used for dispersion agent of the present invention and comprise non-ionic polymer dispersant or anionic polymeric dispersing agent.Non-ionic polymer dispersant comprises and is selected from least a in Z 150PH (PVA), terepthaloyl moietie (EG), USP Kosher, polyoxyethylene glycol (PEG), W 166 (PPG) and the Vinylpyrrolidone polymer (PVP).Anionic polymeric dispersing agent comprises and is selected from least a in ROHM, ammonium polyacrylate and the polyacrylamide toxilic acid (polyacryl maleic acid).Yet the above-mentioned instance of dispersion agent has been merely explanation, and scope of the present invention is not limited to this.
Based on the cerium dioxide as rumbling compound of 100 weight parts, the preferred content of dispersion agent is 0.001 to 10 weight part.More preferably, based on the cerium dioxide of 100 weight parts, the content of dispersion agent is 0.02 to 3.0 weight part.If the content of dispersion agent is less than 0.001 weight part, causes rapid precipitation by low dispersiveness, thereby rumbling compound can not be provided equably because of occurring deposition midway at the transportation polishing slurries.On the contrary; If the content of dispersion agent is greater than 10 weight parts; Near rumbling compound, may form the heavy-gravity dispersant polymer layer that plays similar impact plies effect, this makes that the surface of rumbling compound is difficult to contact with the silica sphere that will polish, and causes polishing rate to descend.
Preferably, be 6 to 8 to make the CMP slurry through cerium oxide powder and dispersion agent being mixed in water then with gained solution titration to pH value.Can be with 1N KOH, 1N HNO 3Deng being used for the titration of pH value.
In case the titration of pH value is accomplished, and preferably the CMP slurry is carried out dispersion stabilization step to improve its dispersion and storage stability.Can adopt dispersion system well known in the art to carry out dispersion stabilization step.For example, can adopt APEX shredder (Kotobuki eng.&mfg.Co., Japan).When adopting the AFEX shredder to carry out dispersion stabilization step; Can adopt and be of a size of 0.01 to 1mm zirconia bead; Can adopt pump that ceria sizing agent is added the AFEX shredder with 10 to 1000ml/min input speed, and can with the mixture of zirconia bead and ceria sizing agent with 2000 to 5000rpm speed in shredder recirculation above 1 to 20 time.
Description of drawings
When combining accompanying drawing, from following detailed description, aforementioned and other purposes, feature and advantage of the present invention will become more obvious, wherein:
Fig. 1 is the photo by the cerium oxide powder of preparation among the embodiment 1 of SEM (sem) shooting;
Fig. 2 is the photo by the cerium oxide powder of preparation among the embodiment 2 of SEM shooting;
Fig. 3 is the photo by the cerium oxide powder of preparation among the embodiment 3 of SEM shooting;
Fig. 4 is the photo by the cerium oxide powder of preparation among the embodiment 4 of SEM shooting;
Fig. 5 is the photo by the cerium oxide powder of preparation in the comparing embodiment 1 of SEM shooting; And
Fig. 6 is for showing the figure of XRD (X-ray diffraction) analytical results of the cerium oxide powder of preparation in embodiment 1 and the comparing embodiment 1.
Embodiment
Now will be at length with reference to preferred implementation of the present invention.It should be understood that following embodiment only is used for explanation, and scope of the present invention is not limited to this.
< embodiment 1 >
At room temperature; Be dissolved in through cerous nitrate and comprise the 100ml terepthaloyl moietie (specific inductivity under 20 ℃: 41.4 0.2mol; Boiling point: 197 ℃) and in the solvent of the mixture of 400ml ethanol (specific inductivity under 20 ℃: 25.3, boiling point: 78.3 ℃), preparation first solution in container; At room temperature, through 0.6mol KOH being dissolved in the solvent that comprises 100ml terepthaloyl moietie and 400ml alcoholic acid mixture preparation second solution in another container; Then, two kinds of solution are mixed each other, and under 50 ℃ temperature, keep.When stirring this mixing solutions, 0.76g hydrogen peroxide (about 30%) splashed into wherein cause deposition and continue 24 hours.Like this, obtain the yellowish brown powder.
XRD analysis has confirmed that the gained powder has the cubic structure of cerium dioxide, and sreen analysis shows that the mean particle size of this powder is 1 to 3 μ m, and the BET measurement shows that this powder has 68m 2The specific surface area of/g.
< embodiment 2 >
The solvent that replaces comprising 100ml terepthaloyl moietie and 400ml alcoholic acid mixture except the solvent that will comprise 400ml terepthaloyl moietie and 100ml alcoholic acid mixture with the solvent that acts on first and second solution; And but not outside precipitating under 50 ℃ the temperature, to make brown ceramic powder with embodiment 1 said identical mode at 120 ℃.
XRD analysis has confirmed that the gained powder has the cubic structure of cerium dioxide, and sreen analysis shows that the mean particle size of this powder is 100 to 300nm, and BET measures and shows that this powder has 113m 2The specific surface area of/g.
< embodiment 3 >
Except in precipitation process with oxygen (O 2) gas is with 0.3cm 3The flow velocity of/min adds in the mixing solutions to replace to wherein splashing into outside the hydrogen peroxide, to make the yellowish brown powder with embodiment 1 said identical mode.
XRD analysis has confirmed that the gained powder has the cubic structure of cerium dioxide, and sreen analysis shows that the mean particle size of this powder is 50 to 100nm, and BET measures and shows that this powder has 52m 2The specific surface area of/g.
< embodiment 4 >
Except in precipitation process with air with 0.5cm 3The flow velocity of/min adds in the mixing solutions to replace to wherein splashing into outside the hydrogen peroxide, to make the yellowish brown powder with embodiment 1 said identical mode.
XRD analysis has confirmed that the gained powder has the cubic structure of cerium dioxide, and sreen analysis shows that the mean particle size of this powder is 50 to 250nm, and BET measures and shows that this powder has 61m 2The specific surface area of/g.
< comparing embodiment 1 >
At room temperature, through the 0.2mol cerous nitrate being dissolved in the solvent that is mixed with 500ml water preparation first solution in container; At room temperature, through 0.6mol KOH being dissolved in the solvent that is mixed with 500ml water preparation second solution in another container; Then two kinds of solution are mixed each other, and be retained under 50 ℃ the temperature.When stirring this mixing solutions, to wherein splashing into 0.76g hydrogen peroxide (about 30%) to cause deposition and to continue 24 hours.Like this, obtain the yellowish brown powder.
XRD analysis has confirmed that the gained powder has the cubic structure of cerium dioxide, and sreen analysis shows that the mean particle size of this powder is several nm to 10nm.
< embodiment 5 >
Prepare the cerium dioxide dispersion soln through mixing each other by the 0.1kg cerium oxide powder of each preparation among the embodiment 1 to 4,0.9kg ultrapure water with based on the dispersion agent of the 2wt% of cerium oxide powder.(Aldrich is Mw2000) as dispersion agent to add polyacrylic acid dispersant.Adopting ammoniacal liquor is 7.5 with cerium dioxide dispersion soln titration to the pH value that makes, and then adopts the APEX shredder that it is carried out the control of improved for dispersion stability and granularity.Use the AFEX shredder under the condition below: zirconia bead is of a size of 0.1mm; Input speed is 400ml/min; And under the speed of 4250rpm, cycle through 5 times.Like this, mean particle size is adjusted to 150 to 300nm.And the mode that contains the polishing particles of 2wt% with dispersion soln adds ultrapure water in this dispersion soln.
For the polishing performance of the CMP slurry of estimating such preparation, to polishing through adopting wafer that PECVD (plasma enhanced chemical vapor deposition) deposited the silicon oxide film of thickness for
Figure G2007800431180D00121
and its to go up the wafer that has deposited the silicon nitride film that thickness is
Figure G2007800431180D00122
through employing LPCVD (low-pressure chemical vapor deposition) on it.Each die attach to the substrate holder of CMP polissoir, and was polished 1 minute, by 100mL/min the CMP slurry that makes is added on the polishing work platform that is stained with the polyurethane polishing liner on it simultaneously.Use 280g/cm 2Pressure substrate holder is pressed to worktable, and substrate holder and worktable rotate with 90rpm respectively wafer polishing the time.In this step, apply 4 pounds of/square inch downward power.In case accomplish polishing,, then adopt film thickness measuring equipment (Nanospec 6100, Nanometric Co., Ltd., the U.S.) to measure the change of polishing front and back film thickness just with the substrate washes clean.
The result of the polishing that the CMP slurry of the cerium oxide powder of each preparation of employing in wherein adding embodiment 1 to 4 and comparing embodiment 1 carries out is listed in the following table 1.
Table 1
Figure G2007800431180D00131
Can find out from table 1, by the cerium oxide powder of each preparation among the embodiment 1 to 4 owing to its excellent polishing rate and selectivity and do not cause tiny cut to show higher polishing performance.Yet, can not carry out the test of CMP polishing performance by the cerium oxide powder of comparing embodiment 1 preparation, because this powder size is too little and intergranular bad dispersibility and can not be prepared to the slurry that is applicable to CMP.
In addition, will be in cerium oxide powder by each preparation in embodiment and the comparing embodiment remaining organic solvent dissolution in pure water, and analyze the carbon content of gained solution.The carbon content that analyzes is converted into the weight ratio with respect to cerium oxide powder, the result is listed in the following table 2.
Table 2
Embodiment 1 Terepthaloyl moietie+ethanol 21ppm
Embodiment 2 Terepthaloyl moietie+ethanol 43ppm
Embodiment 3 Terepthaloyl moietie+ethanol 79ppm
Comparing embodiment
1 Pure water 0.01ppm below
Can find out from The above results; The amount that in the cerium oxide powder that adopts organic solvent by method preparation of the present invention, detects residual residue carbon is 0.1 to 100ppm, and is only adopting pure water not detect residue carbon in as the cerium oxide powder of solvent by the ordinary method preparation.
Fig. 1 to 5 has shown the SEM photo with the cerium oxide powder of comparing embodiment 1 preparation by embodiment 1 to 4.Can find out from these accompanying drawings; Cerium oxide powder by embodiment 1 to 4 preparation has relatively large and uniform grain sizes; And demonstrate multiple granularity according to preparation condition; But by the cerium oxide powder of comparing embodiment 1 preparation is to be that fine particle below the 10nm constitutes by granularity, therefore because intergranular strong agglomeration and be difficult in slurry, to disperse not to be suitable for CMP and polish.
Fig. 6 has shown the result with the XRD analysis of the cerium oxide powder of comparing embodiment 1 preparation by embodiment 1.From accompanying drawing, can find out; Percent crystallinity by the cerium oxide powder of embodiment 1 preparation is superior to the percent crystallinity by the cerium oxide powder of comparing embodiment 1 preparation, therefore even without independent thermal treatment also can with by the cerium oxide powder of embodiment 1 preparation with the rumbling compound that acts on the CMP slurry.
Industrial applicibility
Can know by aforementioned content; The present invention can prepare the mean particle size that has more than the 50nm and the cerium oxide powder of high-crystallinity as solvent through in wet precipitation, adopting organic solvent; And be difficult to prepare such powder through the wet precipitation of routine; Even and without independent thermal treatment, also can be with the cerium oxide powder for preparing like this with the rumbling compound that acts on the CMP slurry.
Owing to adopt the cerium oxide powder of organic solvent preparation to have 50m according to the present invention 2Therefore the specific surface area that/g is above and the granularity of appropriateness control and do not have coarse grain adopt the CMP slurry of this cerium oxide powder preparation to show high polishing rate, and when using it for the CMP method, prevented the minute scratch marks that on polished material, occurs.
Although, it should be understood that the present invention is not limited to disclosed embodiment and accompanying drawing in conjunction with thinking the most practical at present and preferred embodiment having described the present invention.On the contrary, in the essence and scope of accompanying claims, this invention is intended to cover multiple modification and variation.

Claims (10)

1. one kind directly prepares the method for cerium oxide powder in mutually at solution, and this method comprises following step:
A) the cerium precursor solution is mixed with precipitant solution and reaction is taken place; And
B) solution to reaction carries out oxide treatment,
Wherein, at least a water-free pure organic solvent usefulness is acted on the solvent of said cerium precursor solution and precipitant solution, thereby prepare cerium oxide powder, the granularity of this powder is adjusted to 50nm to 3 μ m,
Wherein, said organic solvent is selected from methyl alcohol, ethanol, propyl alcohol, butanols; Glycol; Ether; Ester; Ketone; Formic acid, and its specific inductivity is 20 to 50;
Wherein, said precipitation agent is for being selected from NaOH, KOH and NH 4Alkaline matter among the OH, and
Wherein, step b) comprises step that in the solution of reaction, adds oxygenant or the step that in the solution of reaction, is blown into oxygen-containing gas.
2. method according to claim 1, wherein, the specific inductivity of said ethanol under 20 ℃ is 25.3; Said glycol is a Ucar 35, and butyleneglycol or the specific inductivity under 20 ℃ are 41.4 terepthaloyl moietie.
3. method according to claim 1, wherein, said being reflected at is not less than 30 ℃ and be lower than under the temperature of said solvent boiling point and carry out.
4. method according to claim 1, wherein, said reaction was carried out 30 minutes to 60 hours.
5. method according to claim 1, wherein, the concentration ratio of said cerium precursor solution and precipitant solution is 1: 0.5 to 1: 5.
6. method according to claim 1, this method further are included under 300 to 350 ℃ the temperature the heat treated step of the cerium oxide powder that makes being carried out 10 minutes to 6 hours.
7. method according to claim 1, wherein, the specific surface area of prepared cerium oxide powder is 50 to 200m 2/ g.
8. cerium oxide powder according to each said method preparation in the claim 1 to 7; Through cerium precursor solution and precipitant solution are reacted to each other; Cerium precursor solution and precipitant solution adopt at least a water-free pure organic solvent as solvent separately; And the solution of reaction carried out oxide treatment, and make said cerium oxide powder, wherein; The amount that remains in the surperficial or inner residue carbon of cerium oxide powder is 0.1ppm to 100ppm, and the granularity of this cerium oxide powder is 50nm to 3 μ m.
9. cerium oxide powder according to claim 8, the specific surface area of this powder are 50 to 200m 2/ g.
10. CMP slurry, it comprises the cerium oxide powder that limits like claim 8 as rumbling compound.
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